Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/032—Organic insulating material consisting of one material
  • H05K1/0326—Organic insulating material consisting of one material containing O

Definitions

• the present invention relates to an epoxy resin composition useful as a resin composition for manufacturing copper-clad laminates used for electronic circuit substrates and as an insulating material for electronic circuit substrates.
• Epoxy resins are excellent in insulating properties, electrical characteristics, adhesion, and mechanical characteristics of cured articles, and widely used as insulating materials for printed wiring substrates and as materials for flexible printed wiring boards, but encounter the problems of being fragile, cracking by thermal shock, peeling by external impact, and producing easily cracks by bending because of insufficient flexibility. Although these problems have been hitherto settled by adding rubber-like substances to the epoxy resins, addition of the rubber-like substances causes heat resistance to decrease and adhesion to decrease after heating at a high temperature.
• the present invention aims at solving these problems and providing an epoxy resin composition which has excellent heat resistance and excellent flexibility and which can be appropriately used for laminates, metal foil-clad laminates, insulating materials for build-up substrates, flexible printed wiring boards, materials for flexible printed wiring boards, etc.
• the present inventors have intensively studied to solve the aforesaid problems and accomplished the present invention. That is, the present invention relates to
• An epoxy resin composition characterized by comprising as essential ingredients an epoxy resin (a), an amine curing agent (b), and a phenolic hydroxyl group-containing polyamide-poly(butadiene-acrylonitrile) block copolymer (c),
• x, y, z, l, m, and n are average polymerization degrees, respectively; x represents an integer from 3 to 10, y represents an integer from one to four, z represents an integer from 5 to 15, l+m represents an integer from 2 to 200, m/(m+1) ⁇ 0.04, and n is from 2 to 100,
• An epoxy resin composition characterized by comprising as essential ingredients an epoxy resin (a), a guanidine (b), and a phenolic hydroxyl group-containing polyamide-poly(butadiene-acrylonitrile) block copolymer (c) represented by the following formula:
• x, y, z, l, m, and n are average polymerization degrees, respectively; x represents an integer from 3 to 10, y represents an integer from 1 to 4, z represents an integer from 5 to 15, l+m represents an integer from 2 to 200, m/(m+1) ⁇ 0.04, and n is from 2 to 100,
• An epoxy resin composition characterized by comprising as essential ingredients an epoxy resin (a), diaminodiphenyl sulfone (b), and a phenolic hydroxyl group-containing polyamide-poly (butadiene-acrylonitrile) block copolymer (c) represented by the following formula:
• the epoxy resin (a) used in the present invention includes, for example, (i) glycidyl ether polyfunctional epoxy resins, (ii) glycidyl ester epoxy resins, (iii) glycidyl amine epoxy resins, (iv) alicyclic epoxy resins, and (v) heterocyclic epoxy resins, etc., but are not limited to these.
• the polyfunctional epoxy resins mean epoxy resins having two or more glycidyl groups.
• the glycidyl ether polyfunctional epoxy resins include, for example, (ia) polyfunctional epoxy resins that are glycidyl etherified products of polyphenol compounds, (ib) polyfunctional epoxy resins that are glycidyl etherified products of various novolak resins, and (ic) aliphatic epoxy resins that are glycidyl etherified products of-polyhydric alcohols, etc.
• Polyphenol compounds used as starting materials of the polyfunctional epoxy resins of (ia) include polyphenol compounds such as substituted or unsubstituted bisphenols, for example, unsubstituted bisphenols or bisphenols having lower (C1 to C4) alkyl substituents on benzene ring or/and having halogeno substituents such as fluorine on the alkyl chains, such as bisphenol A, bisphenol F, bisphenol S, tetramethylbisphenol A, dimethylbisphenol A, tetramethyl-bisphenol F, dimethyl-bisphenol F, tetramethylbisphenol S and dimethylbisphenol S, etc.
• polyphenol compounds such as substituted or unsubstituted bisphenols, for example, unsubstituted bisphenols or bisphenols having lower (C1 to C4) alkyl substituents on benzene ring or/and having halogeno substituents such as fluorine on the alkyl chains, such as bisphenol A, bisphenol F, bisphenol S
• the polyfunctional epoxy resins of (ib) include glycidyl etherified products of various novolak resins.
• it includes glycidyl etherified products of various novolak resins such as novolak resins prepared as starting materials from various phenols such as substituted or unsubstituted mono- or polyphenols and substituted or unsubstituted mono- or polynaphthols, phenolnovolak resins containing a xylylene skeleton, phenolnovolak resins containing a dicyclopentadiene skeleton, phenolnovolak resins containing a biphenyl skeleton, phenolnovolak resins containing a fluorene skeleton, phenolnovolak resins containing a phenanthrene skeleton or phenolnovolak resins containing a furan skeleton.
• the substituted or unsubstituted mono- or polyphenols and the substituted or unsubstituted mono- or polynaphthols used as the starting materials of the above novolak resins include, for example, mono- or polyphenols and mono- or polynaphthols that have one to 3 hydroxy groups. These can have substituents other than the hydroxy group.
• the substituents other than the hydroxy group include, for example, unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted alkyl groups having 1 to 10 carbon atoms, halogen atoms, etc., and the substituted alkyl groups having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms which are substituted, for example, by halogen atoms, phenyl group, hydroxy-substituted phenyl groups, etc.
• the alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, etc.
• Typical examples of the mono- or polyphenols and the mono- or polynaphthols include cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.
• the aliphatic epoxy resins of (ic) include, for example, glycidyl etherified products of the following polyhydric alcohols.
• the polyhydric alcohols used as the starting materials of the aliphatic epoxy resins include, for example, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, pentaerythritol, etc.
• the glycidyl ester epoxy resins of the aforesaid (ii) include epoxy resins comprising glycidyl esters of carboxylic acids, preferably dicarboxylic acids.
• the resins include epoxy resins comprising diglycidyl esters of dicarboxylic acids such as hexahydrophthalic acid or phthalic acid, etc.
• the glycidyl amine epoxy resins of the aforesaid (iii) include, for example, epoxy resins where a glycidyl group is introduced into amines, preferably, aromatic amines.
• the resins include epoxy resins where a glycidyl group is introduced into phenylamines such as aniline or toluidine, etc.
• the alicyclic epoxy resins of the aforesaid (iv) include, for example, epoxy resins having C4-C8 cyclorings, preferably C5-C6 cyclorings.
• the resins include alicyclic epoxy resins having an aliphatic skeleton such as cyclohexane, etc.
• the heterocyclic epoxy resins of the aforesaid (v) include, for example, five and six-membered heterocyclic epoxy resins.
• the resins include, for example, heterocyclic epoxy resins having heterocycles such as isocyanuric ring or hydantoin ring, etc.
• epoxy resins used can be appropriately selected depending upon characteristics demanded.
• the glycidyl ether epoxy resins are preferred in general.
• the preferable glycidyl ether epoxy resins are novolak type epoxy resins having a phenol skeleton, novolak type epoxy resins having a triphenylmethane skeleton, and novolak type epoxy resins having a dicyclopentadiene skeleton.
• the novolak type epoxy resins having a phenol skeleton include, for example, bisphenol type epoxy resins (bisphenol A type epoxy resins, bisphenol F type epoxy resins, etc.), phenol novolak type epoxy resins, cresol novolak type epoxy resins, novolak type epoxy resins having a phenol skeleton and a naphthol skeleton, novolak type epoxy resins having a phenol skeleton and a biphenyl skeleton, and phosphate atoms-containing novolak resins having a phosphaphenanthrene skeleton, etc.
• bisphenol type epoxy resins bisphenol A type epoxy resins, bisphenol F type epoxy resins, etc.
• phenol novolak type epoxy resins cresol novolak type epoxy resins
• novolak type epoxy resins having a phenol skeleton and a naphthol skeleton novolak type epoxy resins having a phenol skeleton and a biphenyl skeleton
• Examples of the amine curing agents (b) used in the present invention include aromatic amines such as diaminodiphenyl-methane, diaminodiphenyl sulfone, diamino-diphenyl ether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-diaminonaphthaleneorm-xylylenediamine, aliphatic amines such as ethylenediamine, diethylenediamine, isophorone-diamine, bis(4-amino-3-methyl-dicyclohexyl)methane or polyether diamine, and guanidines such as dicyandiamide or 1-(o-tolyl)biguanide.
• aromatic amines such as diaminodiphenyl-methane, diaminodiphenyl sulfone, diamino-diphenyl ether, p-phenylened
• These amine curing agents (b) are used generally in a range of from 0.3 to 2.0, preferably from 0.4 to 1.6, and further preferably from 0.5 to 1.3 in equivalent ratio of the curing agent to the epoxy group in epoxy resins (a).
• the aforesaid curing agents also can be used as mixtures of two or more thereof.
• the phenolic hydroxyl group-containing polyamide-poly(butadiene-acrylonitrile) block copolymers (c) are used.
• the preferred phenolic hydroxyl group-containing polyamides parts in the block copolymers include, for example, those represented by the following formula
• R represents a divalent residual group of an aliphatic hydrocarbon with 1 to 10 carbon atoms which may have substituents or a divalent residual group where the aforesaid plural, preferably two or three divalent residual groups are linked to one another through crosslinking groups such as —O—, —S—, —SO2—, and —NH—, or a divalent residual group of an aromatic hydrocarbon of 6 to 10 carbon atoms which may have substituents or a divalent aromatic hydrocarbon residual group where the aforesaid plural, preferably two or three aromatic hydrocarbon residual groups are linked to one another through crosslinking groups such as a straight or branched chain alkylene of one to four carbon atoms which may have substituents, —O—, —S—, —SO2—, and —NH—; R 1 represents a residual group of a dicarboxylic acid of 6 to 12 carbon atoms which has at least one phenolic hydroxyl group, for example, a
• 1, m, and n are average polymerization degrees, respectively.
• l+m represents an integer from 2 to 200, m/(m+1) ⁇ 0.04, and n is from 2 to 100, preferably from 2 to 30.
• the ratio of m to 1 is not particularly limited as long as m/(m+1) ⁇ 0.04, the value in general is preferably 0.5 or below.
• the block copolymers (c) are necessary for imparting toughness, adhesion, and flexibility to the cured articles, and the addition thereof can impart excellent toughness without deterioration in heat resistance of the cured articles.
• the amount of the phenolic hydroxyl group-containing polyamides-poly(butadiene-acrylonitrile) block copolymers (c) used is preferably 2 mass % or above to the entire epoxy resin contained in the epoxy resin composition.
• the amount in general is from 10 to 100 mass %, and more preferably from 20 to 80 mass %.
• the ingredient (c) can be synthesized by condensing a dicarboxylic acid ingredient including a phenolic hydroxyl group-containing dicarboxylic acid (in some cases a phenolic hydroxyl group-containing dicarboxylic acid itself) with a diamine ingredient according to ordinary methods as described in United States patents.
• the diamine is added in an excess amount to a dicarboxylic acid ingredient consisting of a phenolic hydroxyl group-containing dicarboxylic acid such as 5-hydroxyisophthalic acid and a dicarboxylic acid containing no phenolic hydroxyl group such as isophthalic acid, and heated with stirring in the presence of a condensing agent (e.g., phosphite esters) and a pyridine derivative in an organic solvent such as N-methyl-2-pyrrolidone in an inactive atmosphere such as nitrogen to carry out condensation reaction, preparing a phenolic hydroxyl group-containing polyamide oligomer.
• a condensing agent e.g., phosphite esters
• a pyridine derivative in an organic solvent such as N-methyl-2-pyrrolidone in an inactive atmosphere such as nitrogen to carry out condensation reaction, preparing a phenolic hydroxyl group-containing polyamide oligomer.
• the ratio of the poly(butadiene-acrylonitrile) copolymer to the polyamide oligomer is not particularly limited, the poly(butadiene-acrylonitrile) copolymer in general is from about 0.1 to about 10 parts to one part of the polyamide oligomer.
• An excess of the dicarboxylic acid is used to the diamine to synthesize a polyamide having carboxyl groups in both terminals and to this, a poly(butadiene-acrylonitrile) copolymer having amino groups in both terminals can be used for blocking. Furthermore, it also is possible to modify the terminals of the polyamide or the poly(butadiene-acrylonitrile) copolymer to react. In this case, one terminal can be modified by a vinyl group and the other terminal by —NH group or —SH group. In the step of synthesizing the ingredient (c), a compound containing a phenolic hydroxyl group in part or all of the diamine can be used.
• the phenolic hydroxyl group-containing dicarboxylic acids composing the dicarboxylic acid ingredient used for the ingredient (c) include, for example, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyphthalic acid, 3-hydroxyphthalic acid or 2-hydroxyterephthalic acid, etc.
• dicarboxylic acids containing no phenolic hydroxyl group include phthalic acid, isophthalic acid, terephthalic acid, dicarboxylnaphthalene, succinic acid, fumaric acid, glutaric acid, adipic acid, 1,3-cyclohexanedicarboxylic acid, 4,4′-diphenyldicarboxylic acid or and 3,3′-methylene-di (benzoic acid), etc.
• the diamine ingredient includes, as phenolic hydroxyl group-containing diamines, 3,3′-diamine-4,4′-dihydroxyphenylmethane, 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)-di-fluoromethane, 3,4-diamino-1,5-benzenediol, 3,3′-dihydroxy-4,4′-diaminobisphenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 2,2-bis(3-amino-4-hydroxyphenyl)ketone, 2,2-bis(3-amino-4-hydroxyphenyl)sulfide, 2,2-bis(3-amino-4-hydroxyphenyl)ether, 2,2-bis(3-amino-4-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)
• diamine containing no phenolic hydroxyl group 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, diaminonaphthalene, piperazine, hexanethylenediamine, tetramethylenediamine, m-xylene-diamene, 4,4′-diaminodiphenylmethane, 4,4′-diamino-benzophenone, 2,2′-bis(4-aminophenyl)propane, 3,3′-diamino-diphenyl sulfone, 3,3′-diaminodiphenyl, etc.
• the diamine ingredient is not limited to these in the present invention.
• Poly(butadiene-acrylonitrile) copolymers having various functional groups in both terminals are marketed by Goodrich Corp. as Hycar CTBN (trade name), and can be used together with the aforesaid phenolic hydroxyl group-containing polyamide oligomers for blocking.
• x, y, z, l, m, and n are average polymerization degrees, respectively, x represents an integer from 3 to 10, y represents an integer from 1 to 4, z represents an integer from 5 to 15, and l+m represents an integer from 2 to 200, m/(m+l) ⁇ 0.04, and n is from 2 to 100, are particularly preferred.
• Curing accelerators can be added as needed to the epoxy resin composition of the present invention.
• the curing accelerators are not particularly limited, and examples thereof include various imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl-imidazole, 2-heptadecylimidazole, 2-phenyl-4-methyl-imidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methyl-imidazole, imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6(2′-methylimidazole(1′))ethyl-s-triazine, 2,4-diamino-6(2′-undecylimidazole(1′)
• Other additives can be added as needed to the epoxy resin composition of the invention.
• the ratios of the other additives are not particularly limited as long as the epoxy resin composition of the invention can be cured.
• the other additives in general can be used as needed in a ratio of from 0 to about 500 mass parts to 100 mass parts of the epoxy resin.
• plasticizers such as natural waxes, synthetic waxes or metal salts of long chain fatty acids; release agents such as acid amides, esters or paraffin; stress relaxation agents such as nitrile rubber or butadiene rubber; inorganic flame retardants such as tin oxide, tin hydroxide, molybdenum oxide, zinc-borate, barium metaborate, aluminum hydroxide, magnesium hydroxide or calcium aluminate; organic flame retardants such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyldiphenyl phosphate, cresyl-2 , 6-dixylylenyl phosphate, 1, 3-phenylene-bis(diphenyl phosphate), 1,3-phenylenebis-(dixylylenyl phosphate), 1,4-phenylene-bis (dixy
• the epoxy resin compositions of the present invention can be prepared by mixing uniformly the epoxy resin (a), the amine curing agent (b), the phenolic hydroxyl group-containing polyamide-poly(butadiene-acrylonitrile) block copolymer (c), as needed the curing accelerator, and other additives.
• the resin composition is appropriately applied depending upon the objective, and cured, for example, by a conventional method such as thermosetting depending upon the curing agent and/or the curing accelerator used.
• a varnish is prepared from the epoxy resin composition of the present invention, applied, for example, by a coating method etc. depending upon the objective, thereafter removed of the solvent as needed, and cured by a method such as thermal curing.
• the varnish is prepared, the epoxy resin (a), the amine curing agent (b), the phenolic hydroxyl group-containing polyamide-poly (butadiene-acrylonitrile) block copolymer (c), as needed the curing accelerator, and other additives than a solvent for varnish are mixed uniformly in the solvent.
• the amount of the solvent in general is not particularly limited as long as the amount makes it possible to coat the varnish. It is preferred to use the solvent so that the solid content in general becomes about 40 to about 80 percent.
• solvent examples include organic solvents such as toluene, ethanol, cellosolve, tetrahydrofuran, N-methyl-2-pyrrolidone or dimethylformamide.
• the varnish thus obtained can be appropriately used as a material for insulating sheets for build-up substrates and insulating material-attached metal foils for build-up substrates and an adhesive for forming flexible printed wiring substrates, cover lay materials, and bonding sheets (hereinafter, these are collectively named materials for flexible printed wiring boards).
• the varnish prepared beforehand (the varnish of the present invention, and so forth) is coated onto a release film by use of a roll coater, a comma coater, etc. This is allowed to pass through an in-line dryer, heated in general at 40 to 160° C. for 2 to 20 minutes to remove the solvent in the varnish, forming an adhesive layer.
• a release film is pressed and bonded on the adhesive-coated surface of the insulating sheet with the adhesive prepared according to the aforesaid process by heated rollers to prepare the insulating sheet.
• the thickness of the coated adhesive in general may be from 40 to 80 ⁇ m in a dry condition.
• the release films usable here include polyethylene film, polypropylene film, TPX (methylpentene copolymer) film, PE (polyethylene) film, polyethylene film with a silicone release agent, polypropylene film and PE film, polyethylene resin-coated paper, polypropylene resin-coated paper, TPX resin-coated paper, etc.
• TPX methylpentene copolymer
• PE polyethylene
• polyethylene film with a silicone release agent polypropylene film and PE film
• polyethylene resin-coated paper polypropylene resin-coated paper
• TPX resin-coated paper etc.
• about the thickness of the release films that of film-based films is preferably from 13 to 75 ⁇ m and that of paper-based films is preferably from 50 to 200 ⁇ m, but the thickness is not particularly limited and can be appropriately determined as needed.
• the varnish prepared before hand is coated onto the metal foil by use of a roll coater, a comma coater, etc. This is allowed to pass through an in-line dryer generally at 40 to 160° C. for 2 to 20 minutes to remove the solvent in the varnish, forming an insulating layer.
• the thickness of the insulating layer coated may be generally from 40 to 80 ⁇ m in a dry condition.
• the metal foil usable here is exemplified by electrolytic copper foil, rolled copper foil, aluminum foil, tungsten foil, iron foil, etc., and the electrolytic copper foil and the rolled copper foil in general are used in view of processability, bending properties, electrical conductivity, etc.
• the thickness of the metal foil in general is from 3 to 70 ⁇ m, it is not particularly limited and appropriately determined depending upon the conditions of application, etc.
• Multilayer printed wiring boards can be obtained by use of the insulating sheet for build-up substrates and the insulating-attached metal foil for build-up substrates thus prepared. Specifically, circuit processing is first carried out on an insulating substrate to form a first circuit, and an insulating layer is formed on the first circuit by applying pressure and heat to the insulating sheet for build-up substrates and/or the insulating material-attached metal foil for build-up substrates by means of a laminator, a press, etc. In order to improve the adhesion between the first circuit and the insulating layer, oxidation-reduction treatment of copper constructing the first circuit or primer treatment by a dilute resin solution before applying pressure and heat to improve impregnating properties can be carried out.
• jointing holes reaching the first circuit are formed on the insulating layer by laser processing and furthermore through holes are formed as needed by a drill or a laser, and thereafter the second circuit is formed on the insulating layer.
• the insulating layer is formed by the insulating sheet for build-up substrates, in order to improve adhesion to electroless plating copper, areas to form the second circuit or the jointing holes are selectively chemically roughened with an acidic oxidizing etching solution such as chrome-sulfuric acid or with an alkaline oxidizing etching solution such as metallic salts of permanganate as a pretreatment, then neutralized, washed with water, added catalyst and, thereafter through these processes, immersed in a plating solution of electroless copper to allow copper to precipitate on the through holes, the non-penetrating jointing holes and the insulating layer until reaching a necessary thickness.
• an acidic oxidizing etching solution such as chrome-sulfuric acid or with an alkaline oxidizing etching solution such as
• Electrolytic plating can be carried out if necessary to increase the thickness. Thereafter, a wiring pattern for the second circuit is formed through etching to prepare a multilayer printed wiring board. Furthermore, it also is possible that areas other than the areas to form the second circuit are masked with plating resist, the areas to form the circuit and the jointing holes are selectively chemically roughened with the aforesaid etching solution to improve adhesion to electroless plating copper, neutralized, washed with water, added catalysts and, after these processes, immersed in a plating solution of electroless copper to allow copper to precipitate on the through holes, the non-penetrating jointing holes and the insulating layer until reaching a necessary thickness to form a wiring pattern, and thereby to prepare a multilayer printed wiring board.
• the jointing holes are selectively chemically roughened with the etching solution as described above, neutralized, washed with water, added catalyst and, thereafter through these processes, immersed in the plating solution of elecroless copper to allow copper to precipitate on the through holes and the non-penetrating jointing holes until reaching a desired thickness. Then, if necessary, the electrolytic plating can be carried out to increase thickness. Subsequently, the wiring pattern for the second circuit is formed through etching or laser processing to prepare a multilayer printed wiring board. A multilayer printed wiring board having further more layers can be made by repeating the aforesaid processes looking upon the second circuit as the first circuit.
• the varnish of the present invention is cured by applying pressure and heat in the above description.
• cold cure caused by a catalyst, oxygen, and moisture at about room temperature, and photo-setting caused by catalysis of acid generated by ultraviolet radiation can be simultaneously used.
• the constitution of the flexible wiring substrates is a three-layer structure consisting of electrical film/adhesive/metal foil.
• the thickness of the adhesive in general is from 10 to 20 ⁇ m, it can be appropriately determined depending upon the conditions of application, etc.
• the leading form of cover lay materials is film-based cover lay coated with an adhesive on one side of a base film.
• the constitution of the film-based cover lay is a three-layer structure consisting of electrical insulative film/adhesive/release film.
• the thickness of the adhesive in general is from 15 to 50 ⁇ m, it can be appropriately determined depending upon the conditions of application, etc.
• cover lay includes dry film type cover lay, liquid type cover lay, etc.
• the dry film type one is of a three-layer structure consisting of release film/adhesive/release film and the adhesive layer doubles as an insulating layer.
• the thickness of the adhesive in general is from 25 to 100 ⁇ m, it can be determined depending upon the conditions of application, etc.
• the insulating layer is made by coating and curing.
• the constitution of the bonding sheet is a three-layer structure consisting of release film/adhesive/release film. Although the thickness of the adhesive in general is from 15 to 50 ⁇ m, it can be appropriately determined depending upon the conditions of application, etc.
• Examples of the aforesaid electrical insulative film usable include polyimide film, PET (polyethyleneterephthalate) film, polyester film, poly(parabanic acid) film, poly(ether ether ketone) film, polyphenylene sulfide film, aramid film, etc.
• polyimide film is preferred in view of heat resistance, dimensional stability, mechanical characteristics, etc.
• the thickness of the films in general ranges from 12.5 to 75 ⁇ m, it is not particularly limited and appropriately determined as needed.
• one side or both sides of these films can be subjected to surface treatment such as low-temperature plasma treatment, corona discharge treatment, sandblast treatment.
• the aforesaid metal foil includes metal foil similar to that usable for the aforesaid metal foil with insulating materials for build-up substrates, and the aforesaid release film includes a release film similar to that usable for the aforesaid insulating sheets for build-up substrates, respectively.
• the varnish of the present invention prepared beforehand is coated onto the aforesaid electrical film by use of a roll coater, comma coater, etc. This is allowed to pass through an in-line dryer and heated at 40 to 160° C. from 2 to 20 minutes to remove the solvent in the varnish, forming an adhesive layer. Subsequently, A release film is pressed and bonded on the adhesive-coated surface of the electrical insulative film with the adhesive by heat rollers.
• the thickness of the adhesive coated is generally from 15 to 50 ⁇ m in a dry condition.
• the varnish prepared beforehand is coated onto a release film by use of a roll coater, comma coater, etc. This is allowed to pass through an in-line dryer and heated at 40 to 160° C. for 2 to 20 minutes to remove the solvent in the varnish, forming an adhesive layer.
• a release film is pressed and bonded on the adhesive-coated surface of the release film with the adhesive by heat rollers.
• the thickness of the adhesive coated is generally from 25 to 100 ⁇ m in a dry condition.
• the viscosity of the varnish is adjusted by adding a solvent so as to become suitable for the coating procedure.
• the varnish prepared beforehand is coated onto a release film by use of a roll coater, comma coater, etc. This is allowed to pass through an in-line dryer and heated at 40 to 160° C. for 2 to 20 minutes to remove the solvent in the varnish, forming an adhesive layer.
• a release film is pressed and bonded on the adhesive-coated surface of the release film with the adhesive by heat rollers.
• the thickness of the adhesive coated may be generally from 15 to 50 ⁇ m in a dry condition.
• the varnish prepared beforehand is coated onto the aforesaid electrical insulative film by use of a roll coater, a comma coater, etc. This is allowed to pass through an in-line dryer and heated at 40 to 160° C. for 2 to 20 minutes to remove the solvent in the varnish, forming an adhesive layer.
• a release film is pressed and bonded on the adhesive-coated surface of the electrical insulative film with the adhesive by heat rollers.
• the thickness of the adhesive coated may be generally from 10 to 20 ⁇ m in a dry condition.
• the resulting reaction solution was poured into 20 liters of methanol to precipitate an aromatic polyamide-poly(butadiene acrylonitrile) block copolymer where the content of poly(butadiene-acrylonitrile) copolymer parts was 50 percent and the phenolic hydroxyl group contained was about 14 mole percent (ingredient (C) of the present invention; hereinafter referred to as polyamide A).
• This precipitated polymer was further washed with methanol and refluxed in methanol to be purified.
• the intrinsic viscosity of this polymer was 0.85 dl/g (dimethylacetamide, 30° C.).
• the IR spectrum of the polymer powder was measured by the diffused reflection method, and absorption based on an amidocarbonyl group was observed at 1674 cm ⁇ 1 , absorption based on the C—H bonds of the butadiene parts was observed at 2856 to 2975 cm ⁇ 1 , and absorption based on the nitrile group was observed at 2245 cm ⁇ 1 , respectively.
• the epoxy resin composition (unit: “part”) shown in the column of Example 1 of Table 1 was dissolved in a mixed solvent consisting of one part of N,N-dimethylformamide (DMF) and one part of methyl isobutyl ketone (MEK) to prepare a varnish where the concentration of the solid content was 60 percent.
• the varnish was inpregnated in glass cloth of 180 ⁇ m in thickness and50 mm ⁇ 50 mm in size (Trade name WEA18W105F115N, Manufactured by Nitto Boseki Co., Ltd.) and the solvent was removed under drying conditions of 130° C. ⁇ 5 minutes and 150° C. ⁇ 2 minutes to obtain a prepreg.
• Prepregs were prepared similarly to Example 1 except that the epoxy resin compositions shown in the respective columns of Examples 2 to 3 and Comparative Examples 1 of Table 1 were used.
• Tg glass transition temperatures
• Epoxy Resin A EPPN-502H (Novolak type epoxy resin having a triphenylmethane skeleton; Manufactured by Nippon Kayaku Co., Ltd.; Epoxy equivalent: 168 g/eq)
• Epoxy Resin B NC-7300L (Novolak type epoxy resin having a phenol skeleton and a naphthol skeleton; Manufactured by Nippon Kayaku Co., Ltd.; Epoxy equivalent: 220 g/eq)
• Epoxy Resin C FX-277BEK75 (Novolak type epoxy resin having a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide skeleton; Manufactured by Toto Kasei K.K.; Epoxy equivalent: 299 g/eq; MEK 25% cut product)
• Epoxy Resin D RE-404S (Bisphenol F type epoxy resin; Manufactured by Nippon Kayaku Co., Ltd.; Epoxy equivalent: 165 g/eq)
• Curing agent A DICY7 (Dicyandiamide; Manufactured by Japan Epoxy Resin K.K.)
• Curing agent B DX147 (Guanidine compound; Manufactured by Japan Epoxy Resin K.K.)
• Curing agent C Diaminodiphenyl sulfone (Manufactured by Wakayama Seika Kogyo; Amine equivalent; 62 g/eq)
• Curing agent D Kayahard TPM (Novolak resin having a triphenylmethane skeleton; Manufactured by Nippon Kayaku Co. Ltd.; Hydroxyl equivalent: 97 g/eq)
• Accelerator A 2-Phenyl-4-methyl-5-hydroxymethyl-imidazole TABLE 2 Comparative Example Example 1 2 3 4 1 2 Tg (° C.) 170 135 165 175 171 170 Bending Test none none none none observed none (Generation of Cracks) Strength for Peeling off 19 20 19 20 16 19 (N/cm) Solder Heat Resistance ⁇ ⁇ ⁇ ⁇ ⁇ Dielectric Constant 3.9 3.9 3.9 3.9 3.8 4.2 (1 MHz)
• the cured articles of the epoxy resin compositions of the present invention are excellent in heat resistance, flexibility, adhesion, dielectric properties, and toughness and very useful for laminates, metal foil-clad laminates, insulating materials for build-up substrates, flexible printed wiring boards, materials for flexible printed wiring boards, etc.

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• 2001
  • 2001-04-20 JP JP2001122259A patent/JP2002080693A/ja active Pending
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  • 2001-06-26 KR KR1020027017616A patent/KR20030034106A/ko not_active Application Discontinuation
  • 2001-06-26 WO PCT/JP2001/005451 patent/WO2002000791A1/ja not_active Application Discontinuation
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